CN105153421A - Method for preparing tetramethyl-1-piperidine-N-oxyl free radical polymer - Google Patents
Method for preparing tetramethyl-1-piperidine-N-oxyl free radical polymer Download PDFInfo
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- CN105153421A CN105153421A CN201510448906.4A CN201510448906A CN105153421A CN 105153421 A CN105153421 A CN 105153421A CN 201510448906 A CN201510448906 A CN 201510448906A CN 105153421 A CN105153421 A CN 105153421A
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Abstract
The invention relates to a catalytic oxidation preparation method of a tetramethyl-1-piperidine-N-oxyl free radical polymer by a two-phase process. The method comprises the following steps of dissolving tetramethylpiperidine (a light stabilizer 944) polymer in an organic solvent to form an organic phase, and forming an aqueous phase from an oxidant and a catalyst; reacting the two phases at 10-85 DEG C for 0.5-20 hours under a stirring state, performing cooling, and separating the liquid; and washing, distilling and drying the organic phase to obtain orange powder. The preparation process technology adopting a two-phase process is high in reacting speed, the catalyst is easily reclaimed and recycled, the product is convenient to extract, and the preparation efficiency of the tetramethyl-1-piperidine-N-oxyl free radical polymer is greatly improved.
Description
Technical field
The present invention relates to a kind of method preparing tetramethyl piperidine nitrogen oxygen free radical polymkeric substance, particularly relate to the preparation method that tetramethyl piperidine nitrogen oxygen free radical polymkeric substance is prepared in the oxidation of a kind of biphasic catalysis.
Background technology
Tetramethyl piperidine nitrogen oxygen free radical (TEMPO) has in fields such as chemistry, biology, foodstuffs industry, agriculturals to be applied comparatively widely.It has functions such as catching free radical, quenching singlet oxygen and selective oxidation.In polymer chemistry, be used as radical scavenger, stopper, antiaging agent, thermal destruction inhibitor and light, thermo-stabilizer, can be also covalency dormancy kind with living chain combined with radical.In organic synthesis, be used as the catalyzer of various alcohol and polyalcohols oxidizing reaction, for being aldehyde by oxidation of primary alcohols, tool highly selective, is no longer oxidizing to carboxylic acid; Secondary alcohol is oxidized to ketone.Tetramethyl piperidine free radical has paramagnetism, is used as ESR spin labeling thing in biological chemistry, is widely used in the research of structure of biological macromolecule and biological respinse mechanism.Relative to micromolecular tetramethyl piperidine nitrogen oxygen free radical, tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO) and high molecular polymer have better consistency.As catalyzer in oxidation system, reacting complete by simple filtration and separable, can be easy to the feature recycled.As can be seen here, tetramethyl piperidine free radical polyalcohol has important practical value and wide application prospect.
At present, great majority research is the synthesis about small molecules tetramethyl piperidine nitrogen oxygen free radical (TEMPO), and also fewer about the research of tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO).TEMPO molecular weight is little, in a lot of solvent, have good solubleness, can be purified, and PIPO is polymkeric substance by recrystallization, and solubleness is relatively little, is difficult to purify, and therefore has requirements at the higher level to building-up process.The synthesis of bibliographical information PIPO is carry out in the homogeneous system of solvent at water, reacts the time (E.G.RozantsevandV.D.Sholle, Synthesis, 1971,401.) of several days.Because tetramethyl piperidine polymkeric substance solubleness in water is less, need a large amount of water to make solvent, reduce the effective concentration of hydrogen peroxide, sluggish, preparation efficiency is lower.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, provide a kind of economy, efficiently prepare tetramethyl piperidine nitrogen oxygen free radical polymer process, using organic compound as solvent, solve raw material photostabilizer 944 problem that solubleness is little in water; By improving temperature of reaction, strengthening mass transfer effect, solving the problem that preparation time is long; Owing to being two phase reaction, catalyzer, in aqueous phase, be can be recycled by separatory, improves the economy of reaction, reduces sewage discharge, is conducive to large-scale production.
Technical scheme of the present invention comprises the steps:
Raw material photostabilizer 944 and organic solvent composition organic phase, oxygenant and catalyzer composition aqueous phase, two-phase, under 10-85 DEG C of uniform stirring, reacts 0.5-20 hour; React complete, separatory is carried out in cooling, and organic phase extremely thoroughly removes a small amount of catalyzer and oxygenant that contain with a small amount of water washing; Then organic phase is distilled again, dry further, obtains orange powder tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO).
Described organic solvent is carboxylicesters or halohydrocarbon; Described carboxylicesters is that R1COOR2, R1 and R2 are respectively methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-; Described halohydrocarbon is halogenated alkane or the chlorobenzene of C1-5.
Described carboxylicesters is preferably ethyl acetate or methyl acetate.
Described halogenated alkane is preferably methylene dichloride, ethylene dichloride or trichloromethane.
Described oxygenant is hydrogen peroxide, and hydrogen peroxide is disposable to add or add in batches or slowly drip with reaction.
In described aqueous phase, the mass concentration of hydrogen peroxide is 0.5-80%.
Described oxygenant quality and photostabilizer 944 mass ratio are 0.3-5:1, and catalyst levels is the 0.1-10% of photostabilizer 944 quality
In described aqueous phase, the mass concentration of hydrogen peroxide is more excellent is 10-30%; The preferred 50-70 DEG C of described temperature of reaction, the reaction times is preferably 3-5 hour.
Described catalyzer is wolframic acid, phospho-wolframic acid, molybdic acid, phospho-molybdic acid or its corresponding sylvite, sodium salt; Catalyzer adds as an aqueous solution.
Described oxygenant and photostabilizer 944 preferred mass are than being 0.7-1.5:1; Catalyst levels is preferably the 0.5-1% of photostabilizer 944 quality.
Advantageous effect of the present invention is as follows:
The present invention, using organic compound as solvent, solves raw material photostabilizer 944 problem that solubleness is little in water; By improving temperature of reaction, strengthening mass transfer effect, solving the problem that preparation time is long; Owing to being two phase reaction, catalyzer, in aqueous phase, be can be recycled by separatory, improves the economy of reaction, reduces sewage discharge, is conducive to large-scale production.This fabricating technology adopts two phase process, and speed of response is fast, and catalyzer is easy to recycling use, and product is convenient to extract, and significantly improves tetramethyl piperidine nitrogen oxygen free radical polymkeric substance preparation efficiency.
Embodiment
Embodiment 1
Take 10g photostabilizer 944, be dissolved in 150mL ethyl acetate, form organic phase; Take 0.1g phospho-wolframic acid, be mixed with the 2.0g aqueous solution, add mass concentration 30% hydrogen peroxide of 15mL, form aqueous phase; Two-phase, under fully stirring, is warmed up to 65 DEG C, reacts 6 hours.Cool to room temperature, separatory, organic phase washed with water three times, steams solvent, obtains 8.7g orange PIPO solid.
Embodiment 2
Take 10g photostabilizer 944, be dissolved in 200mL methylene dichloride, form organic phase; Take 0.5g phospho-wolframic acid, be mixed with the 5.0g aqueous solution and add, add the hydrogen peroxide of 12mL mass concentration 30%, form aqueous phase; Two-phase in abundant stirring, under be warmed up to 35 DEG C, continue reaction 20 hours.Cool to room temperature, separatory, organic phase washed with water three times, steams solvent, obtains 8.6g orange PIPO solid.
Embodiment 3
Take 10g photostabilizer 944, be dissolved in 125mL methyl acetate, form organic phase; Take 0.3g phospho-wolframic acid, be mixed with the 3.0g aqueous solution and add, form aqueous phase; Two-phase, under fully stirring, is warmed up to 65 DEG C, gets 13.5mL mass concentration 30% hydrogen peroxide, slowly drip in 1 hour, continues reaction 3 hours.Cool to room temperature, separatory, organic phase washed with water three times, steams solvent, obtains 8.5g orange PIPO solid.
Embodiment 4
Take 10g photostabilizer 944, be dissolved in 125mL ethyl acetate, form organic phase; Take 0.2g sodium wolframate, be mixed with the 2.0g aqueous solution and add, form aqueous phase; Two-phase, under fully stirring, is warmed up to 65 DEG C, gets 13.5mL mass concentration 30% hydrogen peroxide, slowly drip in 1 hour, continues reaction 6 hours.Cool to room temperature, separatory, organic phase washed with water three times, steams solvent, obtains 8.5g orange PIPO solid.
Embodiment 5
With 0.2g phospho-molybdic acid for catalyzer, other steps are with embodiment 4.
Embodiment 6
With 0.5g Sodium orthomolybdate for catalyzer, other steps are with embodiment 4.
Embodiment 7
Take chlorobenzene as solvent, other steps are with embodiment 4.
Embodiment 8
Reuse for catalyzer with the aqueous phase containing sodium wolframate that separatory in embodiment 6 obtains, other operation stepss are with embodiment 4.
Embodiment 9
Raw material photostabilizer 944 and organic solvent trichloromethane composition organic phase, mass concentration is oxygenant and the tungstic acid catalyst composition aqueous phase of 0.5% hydrogen peroxide, and hydrogen peroxide is disposable to add; Two-phase, under 85 DEG C of uniform stirrings, is reacted 0.5 hour; React complete, separatory is carried out in cooling, and organic phase extremely thoroughly removes a small amount of catalyzer and oxygenant that contain with a small amount of water washing; Then organic phase is distilled again, dry further, obtains orange powder tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO), yield 87%.
The mass ratio of described hydrogen peroxide and photostabilizer 944 is 0.3:1, and catalyst levels is 0.1% of photostabilizer 944 quality.
Embodiment 10
Raw material photostabilizer 944 and organic solvent ethylene dichloride composition organic phase, oxygenant is mass concentration is 80% hydrogen peroxide, and catalyzer is sodium wolframate, oxygenant and catalyzer composition aqueous phase, and hydrogen peroxide adds in batches; Two-phase, under 10 DEG C of uniform stirrings, is reacted 20 hours; React complete, separatory is carried out in cooling, and organic phase extremely thoroughly removes a small amount of catalyzer and oxygenant that contain with a small amount of water washing; Then organic phase is distilled again, dry further, obtains orange powder tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO), yield 85%.
The mass ratio of described hydrogen peroxide and photostabilizer 944 is 5:1, and catalyst levels is 10% of photostabilizer 944 quality.
Embodiment 11
Raw material photostabilizer 944 and organic solvent ethyl acetate composition organic phase, oxygenant is the hydrogen peroxide of mass concentration 10%, and catalyzer is molybdic acid, oxygenant and catalyzer composition aqueous phase, and hydrogen peroxide slowly drips with reaction; Two-phase, under 50 DEG C of uniform stirrings, is reacted 3 hours; React complete, separatory is carried out in cooling, and organic phase extremely thoroughly removes a small amount of catalyzer and oxygenant that contain with a small amount of water washing; Then organic phase is distilled again, dry further, obtains orange powder tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO), yield 87%.
Described hydrogen peroxide and photostabilizer 944 preferred mass are than being 0.7:1; Catalyst levels is preferably 0.5% of photostabilizer 944 quality.
Embodiment 12
Raw material photostabilizer 944 and organic solvent methyl acetate composition organic phase, oxygenant is mass concentration 30% hydrogen peroxide, slowly drips with reaction, and catalyzer is phospho-wolframic acid, adds as an aqueous solution; Oxygenant and catalyzer composition aqueous phase, two-phase, under 70 DEG C of uniform stirrings, is reacted 5 hours; React complete, separatory is carried out in cooling, and organic phase extremely thoroughly removes a small amount of catalyzer and oxygenant that contain with a small amount of water washing; Then organic phase is distilled again, dry further, obtains orange powder tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO), yield 86%.
Described hydrogen peroxide and photostabilizer 944 preferred mass are than being 1.5:1; Catalyst levels is preferably 1% of photostabilizer 944 quality.
Described aqueous phase consists of water, catalyzer, oxygenant.Described oxygenant is hydrogen peroxide, disposablely can add, or adds in batches, or slowly drip; Because hydrogen peroxide decomposes under catalyzer and heating condition, preferably feed postition slowly drips with reaction.
Containing catalyzer in described aqueous phase, reusable, reduce catalyzer cost.Along with access times increase, the water yield increases, and removes portion of water by distillation.The organic solvent of Distillation recovery also can be reused.
In described aqueous phase, the concentration of hydrogen peroxide is 0.5-80%, and concentration is low, and speed of response is slow, and concentration height is dangerous, more preferably selects 10-30%.Because in reaction, part decomposing hydrogen dioxide solution becomes oxygen, the consumption of hydrogen peroxide is greater than theoretical amount.
Described temperature of reaction is 10-85 DEG C; Temperature of reaction is too high, and decomposing hydrogen dioxide solution speed is fast, and effective rate of utilization is low, and temperature of reaction is low, and speed of response is slow, the preferred 50-70 DEG C of temperature of reaction.
Described catalyzer is wolframic acid, phospho-wolframic acid, molybdic acid, phospho-molybdic acid or its corresponding sylvite, sodium salt.Catalyzer promotes decomposing hydrogen dioxide solution, and catalyst levels is large, and speed of response is too fast, and hydrogen peroxide utilization ratio is low, and catalyst levels is low, and speed of response is slow.Catalyst levels is the 0.1-10% of photostabilizer 944 quality, preferred 0.5-1%.In order to make catalyzer fully participate in reaction, more excellently to add as an aqueous solution.
Above about specific descriptions of the present invention, be only not limited to the technical scheme described by the embodiment of the present invention for illustration of the present invention.Those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent replacement, to reach identical technique effect.Needs are used, all in protection scope of the present invention as long as meet.
Claims (10)
1. prepare a tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that comprising raw material photostabilizer 944 and organic solvent composition organic phase, oxygenant and catalyzer composition aqueous phase, two-phase, under 10-85 DEG C of uniform stirring, reacts 0.5-20 hour; React complete, separatory is carried out in cooling, and organic phase extremely thoroughly removes a small amount of catalyzer and oxygenant that contain with a small amount of water washing; Then organic phase is distilled again, dry further, obtains orange powder tetramethyl piperidine nitrogen oxygen free radical polymkeric substance (PIPO).
2. one according to claim 1 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that described organic solvent is carboxylicesters or halohydrocarbon; Described carboxylicesters is that R1COOR2, R1 and R2 are respectively methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-; Described halohydrocarbon is halogenated alkane or the chlorobenzene of C1-5.
3. one according to claim 2 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that described carboxylicesters is preferably ethyl acetate or methyl acetate.
4. one according to claim 2 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that described halogenated alkane is preferably methylene dichloride, ethylene dichloride or trichloromethane.
5. one according to claim 1 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that described oxygenant is hydrogen peroxide, and hydrogen peroxide is disposable to add or add in batches or slowly drip with reaction.
6. one according to claim 5 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that the mass concentration of described hydrogen peroxide is 0.5-80%.
7. one according to claim 1 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, and it is characterized in that described oxygenant quality and photostabilizer 944 mass ratio are 0.3-5:1, catalyst levels is the 0.1-10% of photostabilizer 944 quality.
8. one according to claim 5 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that the mass concentration of hydrogen peroxide in described aqueous phase is more excellent in 10-30%; The preferred 50-70 DEG C of described temperature of reaction, the reaction times is preferably 3-5 hour.
9. one according to claim 1 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that described catalyzer is wolframic acid, phospho-wolframic acid, molybdic acid, phospho-molybdic acid or its corresponding sylvite, sodium salt; Catalyzer adds as an aqueous solution.
10. one according to claim 7 prepares tetramethyl piperidine nitrogen oxygen free radical polymer process, it is characterized in that described oxygenant and photostabilizer 944 preferred mass are than being 0.7-1.5:1; Catalyst levels is preferably the 0.5-1% of photostabilizer 944 quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116478406A (en) * | 2023-04-04 | 2023-07-25 | 浙江精一新材料科技有限公司 | Polysiloxane for light valve and light valve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282645C (en) * | 2001-11-02 | 2006-11-01 | 阿普泰克斯公司 | Processes for the manufacturing of 3-hydroxy-n,1,6-trialkyl-4-oxo-1,4-dihydropyridine-2-carboxamide |
| DE102011110096A1 (en) * | 2011-08-12 | 2013-02-14 | Evonik Röhm Gmbh | Preparing carbonyl compounds comprising an ethylenically unsaturated double bond comprises oxidizing a primary and/or secondary alcohol having an ethylenically unsaturated double bond in the presence of a nitroxyl compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282645C (en) * | 2001-11-02 | 2006-11-01 | 阿普泰克斯公司 | Processes for the manufacturing of 3-hydroxy-n,1,6-trialkyl-4-oxo-1,4-dihydropyridine-2-carboxamide |
| DE102011110096A1 (en) * | 2011-08-12 | 2013-02-14 | Evonik Röhm Gmbh | Preparing carbonyl compounds comprising an ethylenically unsaturated double bond comprises oxidizing a primary and/or secondary alcohol having an ethylenically unsaturated double bond in the presence of a nitroxyl compound |
Non-Patent Citations (3)
| Title |
|---|
| CIHANGIR TANYELI,ET AL.: "Synthesis of polymer-supported TEMPO catalysts and their application in the oxidation of various alcohols", 《TETRAHEDRON LETTERS》 * |
| ROGER A. SHELDON, ET AL.: "Green, catalytic oxidations of alcohols", 《ACCOUNTS OF CHEMICAL RESEARCH》 * |
| 卞惠芳: "2, 2, 6, 6- 四甲基哌啶氮氧自由基的合成", 《天津化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116478406A (en) * | 2023-04-04 | 2023-07-25 | 浙江精一新材料科技有限公司 | Polysiloxane for light valve and light valve |
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